Alkylene oxide condensation products of dimerized fatty acid alylol amides



Q Patented May 10, 1949 UNITED STATES PATENT OFFICE ALKYLENE OXIDECONDENSATION PROD- UCTS F DIMERIZED FATTY ACID AL- KYLOL AMIDES Jack '1.Thurston, Riverside, and Ruth B. Warner,

Stamford, Conn., assignors to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Application June 18, 1946,

Serial No. 677,524

'12 Claims. (01. zoo-4045i This invention relates to water-solublealkylene oxide condensation products of bis-alkylol amides ofheat-polymerized or dimerized polyunsaturated fatty acids ofapproximately 18 carbon atoms, and to their methods of preparation.Objects of the invention are to obtain non-ionic surfaceactive agentshaving good dispersing and emulsimonoor dialkylolamines containingalkylene radicals of 2-4 carbon atoms they are converted into diamidesof the formula RI RI I HO.C,.HQ,..I1I.OC .B.CQ.N.C,,H2...OH in which Ris the residue of the dimerized polyunsaturated fatty acid, n is 2, 3 or4, and R is are essentially organic dicarboxylic acids of thecycloaliphatic series. The most probable structural formulas for thesedimerized fatty acids are given in volume 32 of Industrial EngineeringChemistry, page 808, as follows:

Di-merization of octadecadienic acids and their esters by 1,4-dieneaddition leads to compounds of the following structure, or isomersthereof:

1 1 H o o=conl 1c/ CH (CH2)aC HC-(CH2)7C onucmn- H H OH Conjugated andunconjugated octadecatrienic acids and their esters polymerize by abimolecular addition involving and additional intramolecularring'closure, forming a compound of the following structure, or isomersthereof:

In our copending application Serial No. 677,525 filed concurrentlyherewith we have shown that by heating these compounds or their loweralkyl esters such as the methyl or ethyl esters with either hydrogen orthe I'adiCa1?CnH2n.OH depending on whether the mono or dialkylolaminewas used. These diamides, which vary in appearance from dark, viscousliquids to non-crystalline solids, are soluble in alcohols and inarcmatic hydrocarbon solvents but are insoluble in water and are notsurface-active.

Our present invention is based on the discovery that these bis-alkylolamides can be converted into water-soluble non-ionic agents bycondensing them with sufiicient quantities of alkylene oxides of 2-4carbon atoms to render the product water-soluble. The inventiontherefore consists in the production of watersoluble derivaties ofbis-alkylol amides of dimerized polyunsaturated fatty acids ofapproximately 18 carbon atoms, in which the alkylol radicals contain 2-4carbon atoms, by condensing them with ethylene, propylene or butyleneoxide or similar compounds such as epichlorhydrin which contain awater-solubilizing lower alkylene oxide ring.

' Any polyunsaturated fatty acid of approximately 18 carbon atoms may beused as a starting material in preparing the compositions of the presentinvention. Fatty acid mixtures containing polyunsaturated fatty acids ofapproximately 18 carbon atoms are employed in preparing the dimerized.fatty acids because they are readily obtainable by the hydrolysis ofnatural oils of vegetable and animal origin, and it will be understoodthat the expression dimerized polyunsaturated fatty acids ofapproximately 18 carbon atoms refers to the monomeric fatty acids fromwhich the dimerized acids are prepared by heat treatment rather than tothe resulting dimers, which contain approximately 36 carbon atoms. Thedimer acids may be used either in the form of the free acids or as thelower alkyl esters thereof, such as the methyl, ethyl or propyl esters,in preparing the alkylol amides employed in the process of ourinvention.

Any monoor diahyloloamine in which the alkylene radical or radicalscontain 2-4 carbon atoms may be condensed with the dimerized higherfatty acids described above, or with their methyl, ethyl or propylesters, to form diakylol surface-active 3 amides. Typicaldialkyloloamines which may be used are monoethanolamine, diethanolamine,monopropanolamine, dipropanolamine, monobutanolamine, dibutanolamine ormixed dialkylolamines containing one ethanol and one propanolsubstituent, or one ethanol and one butanol substituent, etc. These andother similar amines may be condensed with the dimerized higher fattyacids by refluxing a solution containing about one mol of the dimerizedacid and two mols of the amine in an organic solvent such as toluene,xylene and the like while distilling oi! the water produced by the amideformation. when esters of the dimerized fatty acid are employed theorganic solvent may be omitted, the two reagents being simply mixed andheated at about 150-200 C. in an inert atmosphere for several hours. Theliberated alcohol may then be removed, together with any excess amine,by distillation at reduced pressures.

The alkylene oxide condensation can be carried out in the absence ofsolvents by heating the dimer acid diamides with ethylene, propylene orbutylene oxide in an autoclave under pressures up to 4-5 atmospheres,preferably in the presence of a small quantity of a catalyst such assodium alcoholate at temperatures of l-160 C. We have found, however, asanother important feature of the invention that the condensationreaction can be carried out at considerably lower pressures andtemperatures, and in most cases at atmospheric pressures, by the use ofpolar solvents such as isopropyl alcohol, tertiary butyl alcohol and thelike, preferably with the addition of a lower alkyl amine such asdiethylamine or trlethylamine as catalyst. Under these conditions,solubilizing amounts of lower alkylene oxides can be condensed with thedimer acid diamides simply by passing the alkylene oxide compound intothe solution under a reflux condenser, and at approximately the .boilingpoint of the solvent used.

The quantity of allwlene oxide to be condensed with the dimer aciddiamides to obtain the proper degree of water-solubility for optimumdispersing, emulsifying or dye-assistant properties may vary throughouta wide range. With diamides of relatively low molecular weight, such asthe bis-monoethano'lamides, as little as 8 mols of ethylene oxide or10-15 mols of propylene oxide or -25 mols of butylene oxide for each molof the dimer acid diamide will produce adequate water-solubility. Asshown in Example 4, as much as 175 mols of alkylene oxide for each molof the dimer acid can'easily be combined if desired.

The invention will be further illustrated by the following specificexamples. It should be understood, however, that although these examplesmay describe in detail certain specific features of the invention, theyare given primarily for purposes of illustration and the invention inits broader aspects is not limited thereto.

Example 1 tend to distill off with the water.

For example, 56 parts by weight of dimerized Example 2 t-Butanol, 300cc., 190 grams of the N,N'-di-2- hydroxyethylamide of the dimer acid ofExample 1 and 20 cc. of triethylamine were heated together in a flaskprovided with stirrer, inlet tube, thermometer, and spiral coil refluxcondenser. Ethylene oxide was bubbled through the resulting solution,maintained under atmospheric pressure, at 70-80 C. until 244 grams wereabsorbed. This required about 12 hours. During the reaction ice waterwas circulated through the reflux condenser to prevent escape of theunreacted ethylene oxide. When the addition was complete the reactionmixture was allowed to reflux for 2 or 3 hours or until the temperaturereached -95 C. after which the solvent and volatile material werestripped at reduced pressure (20-30 mm). The product was 418 grams ofdark, viscous liquid.

Example 3 The ethanolamide of the dimer acid of Example l, 192 grams,225 cc. of t-butanol, and 15 cc. of triethylamine were heated atatmospheric pressure with agitation to 70-80 C., and ethylene oxide wasbubbled through the solution as in Example 2. After 4'77 rams of gas hadbeen absorbed (about 24 hours), the solution was refluxed for 3 hours-The t-butanol and triethylamine were then removed by distillation atreduced pressure. The product was 655 grams of thick, dark brown liquidwhich was soluble in water to form clear foaming solutions.-

Example 4 A mixture of 21 grams of the dimer acid ethanolamine ofExample 1, cc. of t-butanol and 15 cc. of triethylamine were heated withagitation to 7040 C. as in Example 3 and 266 grams of ethylene oxidewere absorbed. The yield was 271 grams of a product containing ethenoxyunits per molecule.

Example 5 A solution of 840 grams (1.5 mols) of dimer- Example 6 A250-gram portion of the product of Example 5 was mixed with 200 cc. oft-butanol and 10 cc. of triethylamine in a flask fitted with stirrer,thermometer, gas inlet tube, and a coil condenser open to the atmospherethrough which ice a clear yellow, foaming solution.

8 water was circulated. Ethylene oxide was passed into the solution at-85 C. for 7 hours at the end of which time 243 grams were absorbed. Re-

fluxing was continued for 2 hours, and the vola-' i Example 7 A mixture.of 200 grams (.342 mol) of the dimethyl ester of dimerized linseed acid(prepared according to Bradley, Industrial & Engi-- neering Chemistry32, 802 (1940)), and 57 grams (.684 mol plus 20% excess of ethanolamine)was heated with stirring at 130-180 C. for two hours in a, nitrogenatmosphere. At the end of this time the excess ethanolamine and themethyl alcohol were distilled off under waterpump pressure up to atemperature of 160 C. The product was a dark red oil. Yield 200 grams,of theory.

Example 8 A mixture of 200 grams (0.36 mol) of dimerized soya bean fattyacid and 60 grams (0.72 mol plus 10% excess of normal propanolamine) andml. of xylene was refluxed with stirring, stripping oil the water in atrap as it formed. The reaction required 12% hours at -148 C. When thereaction was complete, as shown by the fact that no more water formed.the xylene and excess normal propanolamine were stripped off bydistillation under water-pump pressure up to a temperature of C. Theproduct was a viscous greenish-black oil. Yield 243 grams, 100% oftheory.

Example 9 A mixture of 200 grams (0.36 mol) of dimerized soya beam fattyacid, 80 grams (0.72 mol plus 10% excess of z-amino-l-butanol) and 150ml. of xylene was refluxed at a temperature of 145?- C. for 20 hours.Thewater was stripped out in a trap as it formed. When the reaction wascomplete the xylene and excess butanolamine were stripped off underwater-pump pressure up to a temperature of C. The product was a darkgreen viscous oil. Yield 250 grams, 99% of theory.

Example 10 A mixture of 228 grams (0.39 moi) of the dimethyl ester ofdimerized tung oil fatty acid (prepared according to Industrial 8:Engineering Chemistry 32, 802 (1940)) and 60 grams (0.78 mol plus 20%excess) of 95% ethanolamine was heated for two hours at 1'70-180" C. ina nitrogen atmosphere. The excess ethanolamine and the methanol weredistilled off under water-pump pressure up to a temperature of 190 C.The product was an amber colored viscous oil. Yield 253 grams, 100% oftheory.

Example 11 a solution of 97' grams (0.151 mol) of thebis-monoethanolamide of dimerized linseed fatty acid prepared asdescribed in Example '7, 100 ml.

during 3% hours. At the end of this time 125 grams (2.84 mols) had beenabsorbed. The reaction mixture was heated for another three hours duringwhich time the reflux temperature rose to 96 C. The solvent and volatilematerial were distilled off under water-pump pressure up to atemperature of 130 C. The product was a dark red oil, yield 217 grams.

Example 12 A solution of 100 grams (0.156 mol) of thebis-monoethanolamide of dimerized linseed fatty acid, 100 ml. oftertiary butyl alcohol and 10 ml. of triethylamine was placed in theapparatus described in the preceding example. Ethylene oxide was passedinto the solution during 5 hours at a temperature of 6888 C. During thistime 217 grams (4.93 mols) were absorbed. The reaction mixture washeated for an additional three hours and the "reflux temperature rose to95 C. The solvent and volatile materials were distilled oil underwater-pump pressure up' to 130 C. The product was a dark red oil, yield310 grams.

Example 13 A solution of 100 grams (0.156 mol) of thebis-monoethanolamide of dimerized tung fatty acid, 100 ml. of tertiarybutyl alcohol and 10 ml.

of triethylamine was-placed in the apparatus described above. Ethyleneoxide was passed into the solution during 4 hours at a temperature of75-84 C. During this time 129 grams (2.93 mols) were absorbed. Themixture was heated for an additional four hours at 92-95 C. to completethe reaction. The solvent and volatile materials were distilled off asin the preceding examples. The product was a brown viscous oil, yield224 grams. I

Example 14 A solution of '100 grams (0.149 moi) of thebis-monopropanolamide of dimerized cottenseed fatty acid, 100 ml. oftertiary butyl alcohol and 10 ml. of triethylamine was placed in theapparatus described above. Ethylene oxide was passed into the flaskduring seven hours at 80-86 C. During this time grams (3.86 mols) wereabsorbed. The mixture was heated at 95-105 C. for an additional threehours to complete the reaction. The solvent and volatile materials weredistilled oi! as before. The product was-a brown viscous oil, yield 263grams.

Example 16 solution of the product of Example 2 were then added and thebath brought slowly to the boil and maintained there at the boil forsufficient time to complete dyeing. The yarn was then removed, wellrinsed, and dried. The dyeing was bright, level, and of excellent colorvalue.

A dye bath was made up having the same composition as before but withoutthe surface-active agent. The resulting dyeing was definitely inferiorin brightness, levelness and strength of shade.

Example 17 A dye bath was made up of 4000 parts of water heated to 100F. and 100 parts of wool fabric gradually introduced and maintained fora sufficient time .to assure thorough wetting. parts of concentratedsulfuric acid was diluted, added to the dye bath, and allowed topenetrate the wool. Thereupon the solutions of. the following dyes wereintroduced and allowed to disperse:

1 part of the chromium complex of the azo dyestuif obtained fromdiazotized anthranilic acid and 1-(4'-sulfophenyl)-3-methy1 5pyrazolone.

part diazotized 1-amino-2-hydroxy-naphthalene-4-sulfonic acid coupled to1-pheny1-3- methyl-5-pyrazolone I part diazotized1-amino-2-hydroxy-naphthalene-4-sulfonic acid coupled tol-hydroxynaphthalene-8-sulfonic acid Two parts of the product of'Example 2 dissolved in warm water were then added, the temperature ofthe dye bath raised to the boil gradually, and boiled for a sufficienttime to complete dyeing. Thereupon the dye bath was run off, the woolfabric rinsed in cold water, and dried.

The goods dyed were level, free of skitteriness, and showed no oilblotches. The shade of the fabric was strong, approximately 20% strongerthan the same dyeing effected under identical conditions and withoutsurface-active agent.

Example 18 A dye bath was made up of 300 parts of water and 0.4 part ofthe chromium complex of the azo dyestuff obtainedfrom-diazotized1-amino-2- hydroxy-6-nitro-naphthalene 4 sulfonic acid coupled to2-naphthol. 0.5 part of calcined Glaubers salt and 0.1 part of 56%acetic acid were then added, whereupon 5 parts of thoroughly wet outwool yarn were introduced into the dyebath. parts of a 1% solution ofthe product of Example 2 were introduced and the temperature raised to180 F., whereupon 0.075 part of formic acid was added, the temperatureraised to the boil, the bath boiled for a short time, 0.1 part sulfuricacid added and the boil continued for about twice the length of timeuntil dyeing was complete.

Example 19 A dye bath was made up of 300 parts of water and 0.1 part ofwell dissolved chromium complex of the azo dyestuifobtainedfromdiazotized 4 nitro-2-amino-phenol coupled to1-(4'-sulfophenyl)-3-methyl-5-pyrazolone. 3 parts of 10% ammoniumsulfate solution were then added with 4 parts of calcined Glaubers salt.Thereupon 7.5 parts of a 1% solution of the product of Example 11 wereadded and 5 parts of thoroughly wet out wool yarnthen introduced. Thebath was slowly brought to the boil, boiled for a short time, 0.5 partof 56% acetic acid added, boiling continued for about the same length oftime, followed by an addition of another 0.1 part of 56% acetic and theboiling then continued for the same time until the dyeing was complete.The yarn was removed, rinsed and dried, and presented a bright dyeingwhich was level and of excellent color value.

A similar dyeing procedure was followed with no surf ace-active agentadded but all other factors kept the same. The resulting dye was quiteinferior in brightness, levelness and strength of shade.

' What we claim is:

1. Water-soluble condensation products of lower alkylene oxides of '2-4carbon atoms with dialkylolamides of dimerized polyunsaturated fattyacids of the formula Ii R! Ho.c.H1...N.oo.R.co.1 I.c,H:.on wherein R isthe residue of dimerized polyunsaturated fatty acids of approximately 18carbon atoms, 11. is a whole number from 2 to 4 inclusive and R. is amember of the group consisting of hydrogen and 'CnH21|.-OH saidcondensation products having from 8 to 175 mols of said lower alkyleneoxide condensed therein.

2. Water-soluble condensation products of ethylene oxide withdialkylolamides of dimerized polyunsaturated fatty acids of the formulawherein R is the residue of dimerized polyunsaturated fatty acids ofapproximately 18 carbon atoms, 11 is a whole number from 2 to 4inclusive and R is a member of the group consisting of hydrogen andCnH2n.OH, said condensation products having from 8 to 1'15 mols ofethylene oxide condensed therein.

3. Water-soluble condensation products of lower alkylene oxides of 2-4carbon atoms with bis-monoethanolamides of dimerized polyunsaturatedfatty acids of approximately 18 carbon atoms, said condensation productshaving from 8 to mols of said lower alkylene oxide condensed therein.

4. Water-soluble condensation products of lower alkylene oxides of 2-4carbon atoms with bis-diethanolamides of dimerized polyunsaturated fattyacids of approximately 18 carbon atoms, said condensation productshaving from 8 to 1'75 mols .of said alkylene oxide condensed therein.

5. Water-soluble condensation products of ethylene oxide withbis-monoethanolamides of dimerized polyunsaturated fatty acids ofapproximately 18 carbon atoms, said condensation products having from 8to 175 mols of ethylene oxide condenser therein. l

6. Water-soluble condensation products of ethylene oxide withbis-diethanolamides of dimerized polyunsaturated fatty acids ofapproximately 18 carbon atoms, said condensation products having from 8to 1'75 mols of ethylene oxide condensed therein.

'I. A method of producing water-soluble derivatives of dialkylolamidesof dimerized polyunsaturated fatty acids of the formula urated fattyacids of approximately 18 carbon atoms, 1: is awhole number from 2 to 4inclusive and R is a member of the group consisting of hydrogen andC1rH-.m.0H which comprises condensing therewith a sumcient quantityof analkylene oxide of 2-4 carbon atoms to render the product water-soluble,said quantity being from 8 to 175 mols of the alkylene oxide for eachmol of the dimer acid diamide.

' alkylene oxide is ethylene oxide.

11. A method of producing water-soluble derivatives ofbis-diethanoiamides of dimerized polyunsaturated fatty acids ofapproximately 18 carbon atoms which comprises condensing therewith asufiicient quantity of an alkylene oxide of 2-4 carbon atoms to renderthe product watersoluble, said quantity being from 8 to 175 mols of thealkylene oxide for each mol of the dimer acid diamide.

12. A method according to claim 11 in which the alkylene oxide isethylene oxide.

JACK T. THURSTON.

RUTH B. WARNER.

REFERENCES crrnn The following references are of record in the 15 fileof this patent:

' UNITED STATES PATENTS Number Name Date 2,243,329 De Groote et a1 May27, 1941 20 2,344,977 De Groote et a1 Mar. 28, 1944 2,379,413 BradleyJuly 3, 194,5

FOREIGN PATENTS Number Country Date 337,368 Great Britain Oct. 27, 1940364,104 Great Britain Dec. 28, 1931 380,431 Great Britain 1932 802 to809 by Bradley et a1.

